Method for converting a gas comprising carbon monoxide into methane by means of a catalytic material containing praseodymium and nickel on alumina

ABSTRACT

The invention relates to a method for converting a gas into methane (CH 4 ) which includes:
         a step of activating a catalytic material including praseodymium oxide (Pr 6 O 11 ) associated with nickel oxide (NiO) and alumina (Al 2 O 3 ), the respective proportions of which are, relative to the total mass of these three compounds:
           Pr 6 O 11 : 1 wt % to 20 wt %,   NiO: 1 wt % to 20 wt %, and   Al 2 O 3 : 60 to 98 wt %; and   
           a step of passing a gas including at least one carbon monoxide (CO) over the activated catalytic material.

TECHNICAL FIELD OF THE INVENTION

The present invention concerns a method and a device for converting agas into methane.

It applies to the field of the conversion of carbon monoxide (CO) in agas mixture rich in hydrogen, possibly in the presence of carbon dioxide(CO₂), into a mixture rich in methane (CH₄), in a larger range oftemperatures and, in particular, at low temperatures.

STATE OF THE ART

Catalytic materials that contain nickel oxide and alumina are known. Thenickel oxide content is generally high and varies, depending on themethods, from 20% to 50%. The catalytic performance levels of thesematerials are sometimes judged insufficient, especially when thetemperatures of the method are low, for example below 300° C. Inaddition, the thermodynamics show that the lower the reactiontemperature, the higher the methane conversion rate and the lower thelevel of excess reagents. As the commercially available catalysts aremainly active at temperatures higher than 300° C., their conversion rateis limited by the thermodynamics. Lastly, the high nickel content has anadverse effect on the cost price of these materials, and in some caseson how the disposal of the used loads is handled.

The document “Synthesis of lanthanide series (La, Ce, Pr, Eu & Gd)promoted Ni/[gamma]-Al₂O₃ catalysts for methanation of CO₂ at lowtemperature under atmospheric pressure” by Ahmad Waqar et al., CatalystsCommunications, Elsevier, Amsterdam, NL, vol. 100, Jun. 27, 2017, pages121-126, XP085145534, ISSN: 1566-7367, DOI: 10.1016/J.Catcom.2017.06.044 is known.

The document “Nickel Oxide Based Supported Catalysts for the In-SituReactions of Methanation and Desulfurization in the removal of SourGases from Simulated Natural Gas” by Wan Azelee Wan Abu Bakar et al.,Catalysis Letters, Kluwer Academic Publishers, NE, vol. 128, no. 1-2,Nov. 11, 2008, pages 127-136, XP019671959, ISSN: 1572-879X is alsoknown.

The document “Effect of CeO2 addition on Ni/Al₂O₃ catalysts formethanation of carbon dioxide with hydrogen” by Hezhi Liu et al.,Journal of Natural Gas Chemistry., vol. 21, no. 7, Nov. 1, 2012, pages703-707, XP055276014, US, CN ISSN: 1003-9953 (11)60422-2 is also known.

Document WO 00/16901 is also known.

Lastly, the document “CO2/H2 Methanation on Nickel Oxide based Catalystsdopes with Lanthanide Series” by Mohd Hasmizan Razali, Malaysian Journalof Analytical Sciences, vol. 9, no. 3, Jan. 1, 2005 is known.

Each of these documents is restricted solely to converting carbondioxide into methane.

SUBJECT OF THE INVENTION

The present invention aims to remedy all or part of these drawbacks.

To this end, according to a first aspect, the present invention relatesto a method for converting a gas into methane (CH₄), which comprises:

a step of activating a catalytic material including praseodymium oxide(Pr₆O₁₁) associated with nickel oxide (NiO) and alumina (Al₂O₃), therespective proportions of which are, relative to the total mass of thesethree compounds:

-   -   Pr₆O₁₁: 1 wt % to 20 wt %,    -   NiO: 1 wt % to 20 wt %, and    -   Al₂O₃: 60 wt % to 98 wt %; and

a step of passing a gas including at least carbon monoxide (CO) over theactivated catalytic material.

The inventors have discovered that the choice of the combination ofcompounds of the catalytic material and the respective content of eachof these elements, (Pr₆O₁₁, NiO and Al₂O₃), provide a goodperformance/durability/cost compromise when this catalytic material isused for converting carbon monoxide (CO) in a gas mixture rich inhydrogen (H₂), possibly in the presence of carbon dioxide (CO₂), into agas mixture rich in methane (CH₄), for example mainly containing CO, CO₂and H₂, and offering high performance in converting the group consistingof CO and CO₂ at a low temperature, for example at temperatures below300° C.

This catalytic material has a broader operating temperature range thanthe catalytic materials previously known. Because of thermodynamic laws,the conversion of CO and CO₂ is increased, especially at lowtemperatures.

The catalytic material in the strict sense can be in powdery form, inwhich the mean size of the grains varies from 1 to 100 μm, in the formof beads of 100 μm to 1 mm, preferably between 200 and 800 μm and, evenmore preferably, between 200 and 600 μm.

It is noted that the catalyst formed by activating the catalyticmaterial that is the subject of the invention can be used in differentforms other than beads, for example powder, foam (metal or ceramic),coated on ceramic (cordierite, mullite, etc.) or metallic substrates, orceramic filters, extruded with different geometries (single-lobe,three-lobe, etc.), pellets.

In some embodiments, the gas passing over the activated catalyticmaterial also comprises carbon dioxide (CO₂).

In some embodiments, the proportion of carbon monoxide in the gasreaching the activated catalytic material is higher than five percent byvolume in dry gas.

In some embodiments, during the gas passage step, a gas mixture ispassed that mainly contains CO, CO₂ and H₂, with an H₂ content higherthan that of CO and CO₂.

In some embodiments, during the gas passage step, the mean temperatureof the catalytic layer is below 300° C. It is noted that, even thoughthe fluidized bed makes increased exchanges possible, a slighttemperature peak linked to very rapid kinetics remains near the reactionfront.

In some embodiments, the method comprises a step of shaping thecatalytic material into beads with a mean size of between 100 and 1000μm.

In some embodiments, before the activation step, the catalytic materialhas respective proportions, relative to the total mass of these threecompounds, of:

-   -   Pr₆O₁₁: 3 wt % to 15 wt %,    -   NiO: 3 wt % to 15 wt %, and    -   Al₂O₃: 70 wt % to 94 wt %.

In some embodiments, before the activation step, the catalytic materialhas respective proportions, relative to the total mass of these threecompounds, of:

-   -   Pr₆O₁₁: 5 wt % to 12 wt %,    -   NiO: 6 wt % to 12 wt %, and    -   Al₂O₃: 76 wt % to 88 wt %.

In some embodiments, the alumina has a mesoporosity corresponding to amedian diameter of the pores, determined by Hg intrusion porosimetry, ofbetween 3 and 50 nm.

In some embodiments, the alumina has a gamma structure.

In some embodiments, the catalytic material's specific surface areaSStel is between 50 and 300 m²/g.

In some embodiments, the catalytic material's specific surface areaSStel is between 100 and 250 m²/g.

The performance/durability/cost compromise is therefore furtherimproved.

In some embodiments, the step of activating the catalytic materialcomprises heat treatment in the presence of reducing agents.

In some embodiments, the step of activating the catalytic material inthe presence of reducing agents is performed in a temperature range of300-500° C., and preferably 400-500° C.

In some embodiments, the method also comprises

a step of the solubilization of salt precursors of nickel andpraseodymium, separately or in a mixture;

a step of the surface deposition of metal salts on a carrier based onalumina (Al₂O₃); and

a step of thermal decomposition in an atmosphere comprising oxygen andin a temperature range of 350-500° C., for a period of between one hourand four hours.

In some embodiments, the method comprises, before the gas passage step,a step of constituting the gas comprising at least one of the followingsteps:

-   -   pyrolysis of hydrocarbon materials;    -   pyro-gasification of hydrocarbon materials;    -   gasification of hydrocarbon materials;    -   co-electrolysis of CO₂/H₂O;    -   Water-Gas-Shift; and    -   Reverse Water-Gas-Shift.

These different steps provide a gas comprising carbon monoxide.

In some embodiments, during the step of passing the gas over thecatalytic material, the gas goes through a catalytic layer of activatedcatalytic material.

In some embodiments, the catalytic layer is preferably a bed fluidizedby the passage of the gas through the catalytic material.

In some embodiments, at least one heat exchange tube is immersed in thecatalytic layer.

Each heat exchange tube makes it possible to control the temperature ofthe methanation reaction. The particular catalytic material of theinvention enables an efficient conversion at an average temperature ofless than 300° C., favorable to both the speed of the reaction and itsyield.

According to a second aspect, the present invention relates to a methodfor preparing a catalyst, which comprises:

-   -   a step of the solubilization of salt precursors of nickel and        praseodymium, separately or in a mixture;    -   a step of the surface deposition of metal salts on a carrier        based on alumina (Al₂O₃);    -   a step of thermal decomposition in an atmosphere comprising        oxygen; and    -   a step of activating the material obtained by heat treatment in        the presence of reducing agents.

According to a third aspect, the present invention relates to a devicefor converting a gas into methane (CH₄), which comprises:

-   -   a catalytic layer obtained by activating a catalytic material        including praseodymium oxide (Pr₆O₁₁) associated with nickel        oxide (NiO) and alumina (Al₂O₃), the respective proportions of        which are, relative to the total mass of these three compounds:    -   Pr₆O₁₁: 1 wt % to 20 wt %,    -   NiO: 1 wt % to 20 wt %, and    -   Al₂O₃: 60 wt % to 98 wt %; and

a means for passing a gas including at least carbon monoxide (CO) overthe catalytic layer.

In some embodiments, the catalytic material has respective proportions,relative to the total mass of these three compounds, of:

-   -   Pr₆O₁₁: 5 wt % to 12 wt %,    -   NiO: 6 wt % to 12 wt %, and    -   Al₂O₃: 76 wt % to 88 wt %.

In some embodiments, the device comprises a fluidized bed comprising thecatalytic layer.

In some embodiments, the device comprises at least one heat exchangetube immersed in the catalytic layer.

As the particular features, advantages and aims of this device aresimilar to those of the conversion method that is the subject of theinvention, they are not repeated here.

BRIEF DESCRIPTION OF THE FIGURES

Other advantages, aims and features of the present invention will becomeapparent from the description that will follow, made, as a non-limitingexample, with reference to the drawings included in an appendix, inwhich:

FIG. 1 is a block diagram of a particular production method of thecatalytic material that is the subject of the invention;

FIG. 2 represents, in the form of a logical diagram, a particularembodiment of the method of preparing the catalytic material that is thesubject of the invention; and

FIG. 3 represents a methanation unit utilizing the method that is thesubject of the invention.

DESCRIPTION OF EXAMPLES OF REALIZATION OF THE INVENTION

The present description is given in a non-limiting way, eachcharacteristic of an embodiment being able to be combined with any othercharacteristic of any other embodiment in an advantageous way.

All the contents are, in the description, expressed as a percentage bymass for the solids, and the contents of the gases are expressed as apercentage by volume in dry gas.

The catalytic material utilized by the method that is the subject of theinvention comprises praseodymium oxide (Pr₆O₁₁) associated with nickeloxide (NiO) and alumina (Al₂O₃), the respective proportions of whichare, relative to the total mass of these three compounds:

-   -   Pr₆O₁₁: 1 wt % to 20 wt %, preferably 3 wt % to 15 wt %, and,        even more preferably, 5 wt % to 12 wt %;    -   NiO: 1 wt % to 20 wt %, preferably 3 wt % to 15 wt %, and, even        more preferably, 6 wt % to 12 wt %; and    -   Al₂O₃: 60 wt % to 98 wt %, preferably 70 wt % to 94 wt %, and,        even more preferably, 76 wt % to 88 wt %.

Preferably, the alumina is mesoporous and preferably has a gammastructure. The mesoporosity range of the preferential alumina has amedian diameter of the pores, determined by Hg intrusion porosimetry, ofbetween 3 and 50 nm, and preferably between 5 and 25 nm.

The catalytic material's specific surface area SStel is preferablybetween 50 and 300 m²/g, and more preferably between 100 and 250 m²/g.

The inventors have discovered that the choice of this combination ofcompounds and the respective content of each of these elements, (Pr₆O₁₁,NiO and/or Al₂O₃) provide a good performance/durability/cost compromisewhen this catalytic material is used for converting carbon monoxide (CO)in a gas mixture rich in hydrogen (H₂), possibly in the presence ofcarbon dioxide (CO₂), into a gas mixture rich in methane (CH₄), and, inparticular, to conversions at low temperatures, for example below 300°C. on average in the reaction medium.

This conversion is also called methanation or the Sabatier reaction, andconsists of hydrogenating the CO and/or CO₂ to produce a gas containingCH₄.

Preferably, the conversion is performed based on a gas mixture thatmainly contains carbon monoxide (CO), carbon dioxide (CO₂) and hydrogen(H₂), in particular with a hydrogen (H₂) content higher than that of thecarbon monoxide (CO) and carbon dioxide (CO₂).

The conversion can be performed effectively at an average temperature,in the reaction medium, below 300° C., unlike catalysts previouslyknown.

Different methods can be used to prepare the catalytic material.

In some embodiments, the catalytic material production method comprises,as shown in FIG. 2:

-   -   a step 30 of the solubilization of salt precursors of nickel and        praseodymium, separately or in a mixture;    -   a step 35 of the surface deposition of metal salts on a carrier        based on alumina (Al₂O₃);    -   a step 40 of thermal decomposition in an atmosphere comprising        oxygen and, possibly, of the dehydration of an alumina hydrate        leading to an alumina in gamma or delta form; and    -   a step 50 of activating the material obtained by heat treatment        in the presence of reducing agents.

The step 30 consists of solubilizing, separately or in a mixture, thebase materials of the salt precursors of nickel and praseodymium. Duringthe step 35, a surface deposition of these metal salts is performed on acarrier based on alumina, generally alumina (Al₂O₃) or boehmite-typealumina hydrate (AlOOH). During the step 40, a heat treatment isperformed in an atmosphere comprising oxygen, for example in air or inoxygen, making it possible to decompose the metal precursors and obtainalumina in gamma or delta form when the carrier employed is initiallyboehmite-type alumina hydrate (AlOOH).

In the embodiments of the method described below, the surface depositionof the salt precursors of nickel and praseodymium is performed on acarrier comprising alumina, preferably already in gamma or delta form,or on a boehmite-type alumina hydrate carrier, which leads to an aluminain gamma or delta form when it is dehydrated during the heat treatmentstep.

In the case of thermal decomposition in air, this is performed in atemperature range of 300-800° C., preferably 400-600° C., and, even morepreferably, 350-500° C., preferably for a length of time of between onehour and four hours.

During the step 45, a catalyst is formed based on the catalytic materialobtained during the step 40. During the step 50, the catalyst isactivated. This activation by heat treatment in the presence of reducingagents or by chemical treatment partially or fully transforms the nickeloxide into nickel. The step of activating the catalytic material ispreferably performed in the presence of reducing agents, in atemperature range of 300-500° C. and preferably 400-500° C.

During the step 55, the catalyst is used by passing a gas includingcarbon monoxide (CO) and hydrogen (H₂) over the activated catalyticmaterial, possibly in the presence of carbon dioxide.

A first method example comprises the co-impregnation of praseodymiumsalts 15 and nickel salt 10 on a carrier 20 (see FIG. 1), during a step35 (see FIG. 2). The carrier is, for example a boehmite-type aluminahydrate, or alumina (Al₂O₃) crystallized in gamma or delta form. Thesalts used can be chlorides, nitrates, acetates, or sulfates.

Each of the above-mentioned Ni and Pr salts is solubilizedsimultaneously under agitation, in order to form a homogeneous solution(step 30) which is then put in contact with the carrier (step 35). Thesolution of these metal precursors is then absorbed in the porosity ofthe carrier.

For example, the nickel salt takes the hydrated form Ni(NO₃)₂, 6H₂O, andthe praseodymium salt takes the form Pr(NO₃)₃, 5H₂O.

Such an impregnation can be performed:

-   -   “dry”: the volume of prepared solution is therefore less than or        equal to the volume that can be absorbed by the carrier; or    -   by excess solvent: in that case, a drying phase is necessary.

The impregnated carriers then undergo calcination (step 40) in order tothermally decompose the metal precursors, and form the Ni and Pr oxides.In the case where boehmite-type alumina hydrate is used, the calcinationstep transforms the alumina hydrate into alumina.

A second method example of the preparation of the catalytic materialcomprises successive impregnations of nickel salts then praseodymiumsalts, or praseodymium salts then nickel salts, on alumina or onboehmite-type alumina hydrate.

The selected metal salts of nickel and praseodymium are solubilizedseparately. The solution containing the salt of the first metal (nickelor praseodymium, respectively) is then impregnated on the carrier asdescribed in the first method example, dry or by excess solvent.

A calcination step then makes it possible to decompose the metalprecursor in order to form an intermediate product and possiblytransform the alumina hydrate into alumina. The latter is thenimpregnated by the second solution containing the salt of the secondmetal (praseodymium or nickel, respectively) by again following the samesteps.

A third method example of the preparation of the catalytic materialcomprises co-precipitation of the nitrate salts of praseodymium, nickeland alumina or boehmite-type alumina hydrate, also followed by thermaldecomposition.

A fourth method example of the preparation of the catalytic materialcomprises atomization of a suspension containing salts of nickel,praseodymium and boehmite or alumina, followed by a step of calcinationin air.

During the drying by atomization, the suspension is sprayed as finedroplets by means of an atomizer turbine, or by high pressure injectionthrough nozzles, into a vertical cylindrical chamber swept by a flow ofhot air. Evaporation of the water leads to the formation of a dry powdercollected in the bottom portion of the equipment. This drying methodmakes it possible to form a catalytic material with a targeted particlesize, dependent on the atomization parameters and the characteristics ofthe equipment.

In all the methods for the preparation of the catalytic materialmentioned above, the oxide obtained from the calcination step (step 40)is activated in a reducing gas (CO, H₂, NH₃, etc.) that is pure ordiluted with an inert gas (Ar, N₂, He, etc.), following a suitabletemperature profile, to transform all or part of the nickel oxide (NiO)into dispersed metallic Ni during a step 50.

With respect to the suitable profile, for example, the catalyticmaterial is activated in a flow of a gas containing hydrogen during atemperature profile comprising increasing the ambient temperature to400° C. with a ramp of 2° C./min, and a four-hour plateau at 400° C.,preferably in the presence of reducing agents. More generally, theactivation step is preferably performed in a temperature range of300-500° C. and preferably 400-500° C.

The catalytic material in the strict sense can be in powdery form, inwhich the mean size of the grains varies from 1 to 100 μm. The catalyticmaterial can be in different forms (step 45): powder, foam (metal orceramic), coated on ceramic (cordierite, mullite, etc.) or metallicsubstrates, or ceramic filters, extruded with different geometries(single-lobe, three-lobe, etc.), beads, pellets, etc.

In the case of beads, for example spherical or oblong, preferably, theirmean size is between 100 μm and 1 mm, preferably between 200 and 800 μmand, even more preferably, between 200 and 600 μm.

A step (step 55) of using the catalytic material comprises theconversion of carbon monoxide (CO) into methane, in the presence ofhydrogen (H₂), possibly in the presence of carbon dioxide (CO₂).

Preferably, the gas to be converted comprises at least 5% CO (volumecontent in dry gas), more preferably at least 10% CO (volume content indry gas) and, even more preferably, 15% CO (volume content in dry gas).

15% CO (volume content in dry gas) corresponds, for example, to theminimum CO content usually measured in a gas from steam gasification.

FIG. 3 shows a fluidized-bed reactor including the catalyst and leadingto the conversion of a gas including at least carbon monoxide (CO) intomethane (CH₄), during the passage of this gas over the catalyst, i.e.the activated catalyst material.

For clarity, a fluidized bed enables a category of solids, here thecatalyst, to be given certain properties of fluids, liquids or gases. Itallows a strong interaction of catalyst particles and the gas traversingit. The principle of the fluidized bed is to inject a pressurized gasunder a bed of solid particles. This gas lifts and disperses the solidparticles. It enables more effective catalysts. This is known as afluidized bed reactor (FBR).

The particle agitation and hydrodynamic mixing by flows of gaseousbubbles make the fluidized layers volumes in which the solid particlesare vigorously agitated. There they can exchange heat and material veryeffectively, by direct contact, on a large specific surface, with thegas or with an immersed heat exchanger with a view to reusing orremoving the heat produced by the gas conversion reaction when gascontaining carbon monoxide is converted into methane. The fluidizedlayer therefore constitutes an open volume, practically isothermal,because of the high specific heat capacity by mass of the solidscompared to that of the gas, and by their renewal on contact with theexchange surfaces.

FIG. 3, which is not to scale, shows a schematic view of an embodimentof the reactor 100. This reactor 100 comprises a chamber 105 having onelongitudinal extremity 107, referred to as “lower”, and one oppositelongitudinal extremity 106, referred to as “upper”. The chamber 105 is,for example, formed of a closed, sealed volume. The internal and/orexternal shape of the chamber 105 is not important for the presentinvention, provided the chamber is sealed. For example, the chamber 105has a tubular shape, i.e. a cylindrical shape, which can be oblong asshown in FIG. 3.

The chamber 105 comprises, near the lower extremity 107, an inlet 110 ofgas including carbon monoxide and hydrogen, and possibly carbon dioxide.The chamber 105 comprises, near the upper extremity 106, an outlet 115for methane or for a gas rich in methane. An activated catalyst material125, not consumable by the conversion reaction, forms a catalytic layerwhich is preferably a fluidized bed through which the gas coming fromthe inlet 110 passes.

The inlet, 110 is, for example, an injection nozzle, a nozzle, aperforated tube, a network of piping equipped with strainers. However,any fluid injector usually used in a reactor can be used to realize theinlet 110. The outlet 115 is, for example, an opening formed in thechamber 105 connected to a methane transport line.

In some variants, the reactor 100 comprises heat exchange tubes (notshown) immersed in the chamber 105 and traversed by a fluid having atemperature compatible with the nominal operating temperature inside thechamber 105 during the operation of the reactor 100. The fluid'stemperature is lower than the interior of the chamber to enable thetemperature of the reactor to be maintained by removing excess heatlinked the exothermicity of the conversions utilized. Preferably, thisremoved excess heat is reused.

The average temperature of the reaction medium 125 and/or the outputtemperature of the catalytic layer 115 can be below 300° C. Theexothermic reaction tends to raise the temperature and, in somepreferred embodiments, the temperature of the reaction area iscontrolled to keep it, on average, below 300° C., which favors thethermodynamics while making the reaction possible. In this way areaction with an increased yield is obtained.

Preferably, the pressure inside the chamber 105 is between one bar(atmospheric pressure) and 70 bar, preferably between 1 bar and 20 bar,and, more preferably, between 1 bar and 10 bar. These pressures optimizethe conversion by minimizing the upstream compression costs.

Preferably, the fluidization/flow rate range is between one and sixteentimes the minimum fluidization speed, preferably between two and eighttimes the minimum fluidization speed, which optimizes the heat exchange.

With respect to the source of the CO, CO₂, or hydrogen, the reactor canbe preceded by a pyrolysis unit for hydrocarbon materials (biomass,waste, carbon, etc.), a pyro-gasification unit for hydrocarbon materials(biomass, waste, carbon, etc.), a gasification unit for hydrocarbonmaterials (biomass, waste, carbon, etc.), a Water-Gas-Shift unit, aReverse Water-Gas-Shift unit, or a CO₂/H₂O co-electrolysis unit, asdescribed in patent application EP 16757688.3, included here asreference. For clarity, Water-Gas-Shift (WGS) is a means for adjustingCO content, and Reverse Water-Gas-Shift is a means for producing CO at ahigh temperature from a H₂+CO₂=CO+H₂O mixture (inverse of theWater-Gas-Shift (WGS) reaction).

As an example, the catalyst utilized by the method of the inventionoffers activity at 250° C., higher than commercially availabletechnology (Reference technology having a composition of 50% nickel onalumina, with no praseodymium), as the following table shows:

Test conditions: temperature 250° C., atmospheric pressure, hourlyvolumetric flow rate = 10,000 h⁻¹. Composition of the gas flow: 12% CO,8% CO₂, 70% H₂, 5% H₂O, 5% CH₄. Commercially Catalyst of the inventionavailable catalyst CO conversion  95% 25% CO₂ conversion 7.5%  0%

To be active in methanation, the catalyst must undergo a reductiontreatment that modifies the oxidation state of the Ni and Pr. In theexample presented here, the catalytic material has undergone a reductiontreatment in a gas flow containing hydrogen at 450° C. during afour-hour period.

It is noted that the catalyst formed with the catalytic material is atleast as effective as the commercially available catalyst for averagetemperatures, in the reaction medium, higher than 300° C.

The catalytic material therefore has a broader operating temperaturerange, 220-400° C., preferably 250-350° C.

In this comparative test, the catalyst utilized by the method of theinvention is the catalyst of its most preferred embodiments.

The conversion rates are defined by the ratios ([CO or CO₂]_(input)-[COor CO₂]_(output))/([CO or CO₂]_(input)).

The invention therefore applies particularly well to the field of theconversion of carbon monoxide (CO), possibly in the presence of carbondioxide (CO₂) and a gas mixture rich in hydrogen, into a mixture rich inmethane (CH₄), and, in particular, to conversions at low temperatures.

1. A device for converting a gas into methane (CH₄), which comprises: afluidized bed comprising a catalytic layer obtained by activating acatalytic material including praseodymium oxide (Pr₆O₁₁) associated withnickel oxide (NiO) and alumina (Al₂O₃), the respective proportions ofwhich are, relative to the total mass of these three compounds: Pr₆O₁₁:1 wt % to 20 wt %, NiO: 1 wt % to 20 wt %, and Al₂O₃: 60 wt % to 98 wt%; and an inlet for passing a gas including at least carbon monoxide(CO) over the catalytic layer.
 2. The device according to claim 1, whichcomprises at least one heat exchange tube immersed in the catalyticlayer.
 3. The device according to claim 1, wherein the gas passing overthe activated catalytic material also comprises carbon dioxide (CO₂). 4.The device according to claim 1, wherein the proportion of carbonmonoxide in the gas reaching the activated catalytic material is higherthan five percent by volume in dry gas.
 5. The device according to claim1, wherein, the gas passed is a mixture that mainly contains CO, CO₂ andH₂, with an H₂ content higher than that of CO and CO₂.
 6. The deviceaccording to claim 1, wherein the mean temperature of the catalyticlayer is below 300° C. during the conversion of the gas into methane. 7.The method according to claim 1, wherein the catalytic material presentsa bead shape with a mean size of between 100 and 1000 μm.
 8. The deviceaccording to claim 1, wherein the catalytic material has respectiveproportions, relative to the total mass of these three compounds, of:Pr₆O₁₁: 3 wt % to 15 wt %, NiO: 3 wt % to 15 wt %, and Al₂O₃: 70 wt % to94 wt %.
 9. The device according to claim 1, wherein the alumina has amesoporosity corresponding to a median diameter of the pores, determinedby Hg intrusion porosimetry, of between 3 and 50 nm.
 10. The deviceaccording to claim 1, wherein the alumina has a gamma structure.
 11. Thedevice according to claim 1, wherein the catalytic material's specificsurface area SStel is between 50 and 300 m²/g.
 12. The device accordingto claim 1, wherein the catalytic material's specific surface area SStelis between 100 and 250 m²/g.
 13. The device according to claim 1,comprising a unit for heat treatment in the presence of reducing agentsto activate the catalytic layer.
 14. The device according to claim 13,wherein the temperature range of the heat treatment is of 300-500° C.,and preferably 400-500° C.
 15. The device according to claim 1, whichfurther comprises a catalytic material preparation unit comprising: ameans of the solubilization of salt precursors of nickel andpraseodymium, separately or in a mixture; a means of surface depositionof metal salts on a carrier based on alumina (Al₂O₃); and a means ofthermal decomposition in an atmosphere comprising oxygen and in atemperature range of 350-500° C., for a period of between one hour andfour hours.
 16. The method according to claim 1, which furthercomprises, before the gas passage, a unit for constituting the gascomprising at least one of: a pyrolysis unit for hydrocarbon materials;a pyro-gasification unit for hydrocarbon materials; a gasification unitfor hydrocarbon materials; a CO₂/H₂O co-electrolysis unit; awater-Gas-Shift unit; and a reverse Water-Gas-Shift unit.
 17. The deviceaccording to claim 1, comprising an outlet for the gas passed over thecatalytic layer; the inlet and outlet being positioned on either sidethe catalytic layer, the gas passed going through a catalytic layer ofactivated catalytic material.
 18. The device according to claim 1,comprising an outlet for the gas passed over the catalytic layer; theinlet and outlet being positioned on either side the catalytic layer,the gas passed going through a fluidized bed of activated catalyticmaterial.
 19. The device according to claim 1, wherein the catalyticmaterial consists of praseodymium oxide (Pr₆O₁₁) associated with nickeloxide (NiO) and alumina (Al₂O₃), the respective proportions of whichare, relative to the total mass of these three compounds: Pr₆O₁₁: 1 wt %to 20 wt %, NiO: 1 wt % to 20 wt %, and Al₂O₃: 60 wt % to 98 wt %;